Investigation of N₂ adsorption on Fe₃O₄(001) using ambient pressure X-ray photoelectron spectroscopy and density...

Reactions on iron oxide surfaces are prevalent in various chemical processes from heterogeneous catalysts to minerals. Nitrogen (N₂) is known to dissociate on iron surfaces, a precursor for ammonia production in the Haber-Bosch process, where the dissociation of N₂ is the limiting step in the reaction under equilibrium conditions. However, little is known about N₂ adsorption on other iron-based materials, such as iron oxide surfaces that are ubiquitous in soils, steel pipelines, and other industrial materials. An atomistic description is reported for the binding of N₂ on the Fe₃O₄(001) surface using first principles calculations with ambient pressure X-ray photoelectron spectroscopy. Two primary adsorption sites are experimentally identified from N₂ dissociation on Fe₃O₄(001). The electronic signatures associated with the valence band region unambiguously show how the electronic structure of magnetite transforms near ambient pressures due to the binding of atomic nitrogen to different surface sites. Overall, the experimental and theoretical results of our study bridge the gap between ultra-high vacuum studies and reaction conditions to provide insight into other nitrogen-based chemistry on iron oxide surfaces that impact the agriculture and energy industries.